US5939544A - Process for activating polysaccharides, polysaccharides produced by this process, and use thereof - Google Patents

Process for activating polysaccharides, polysaccharides produced by this process, and use thereof Download PDF

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US5939544A
US5939544A US08/913,782 US91378297A US5939544A US 5939544 A US5939544 A US 5939544A US 91378297 A US91378297 A US 91378297A US 5939544 A US5939544 A US 5939544A
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cellulose
polysaccharide
process according
ammonia
pressure
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Ties Karstens
Hans Steinmeier
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Cerdia Produktions GmbH
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Rhodia Acetow GmbH
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/06—Rendering cellulose suitable for etherification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives

Definitions

  • the invention relates to a process for activating polysaccharides, with which the polysaccharide starting material is brought in contact with liquid ammonia at a starting pressure higher than atmospheric pressure and at a temperature of at least about 25° C., wherein the quantity of liquid ammonia suffices to at least wet the surface of the polysaccharide starting material, and the mixture is subsequently subjected to a pressure release, as well as to activated polysaccharides made by this process.
  • Cellulose is a linear polysaccharide built up from glucose monomer units.
  • the smallest macroscopic structural elements of native cellulose are elementary crystallites, which consist of parallel aggregated cellulose molecules. Because of the macromolecular nature of the molecules, many of these elementary crystallites are linked by random molecule segments into long strands, the elementary fibrils. These elementary fibrils can join up along a variable length into secondary aggregations. The length of the secondary aggregations and the aggregation degree are important structural characteristics.
  • cellulose Prior to certain further processing steps, e.g. prior to the etherification, cellulose must be activated. Depending on the processing conditions it may happen that no homogeneous activation of the cellulose takes place, because the crystalline regions are poorly accessible to the activating agents that are used. It is known to activate cellulose by swelling it with liquid ammonia (see H. A. Krassig, Cellulose Structure, Accessibility and Reactivity, Gordon and Breach Science Publishers, 1992). The ammonia molecule, because of its free electron pair on the nitrogen atom, can compete with hydroxyl groups of adjoining molecule chains and substitute OH--O--hydrogen bridges by OH--N bonds.
  • ammonia-cellulose complexes are formed.
  • the formed ammonia-cellulose complexes are relatively unstable. When evaporating the ammonia, the triple growth in fibre diameter returns to its original dimensions. The complex is also destroyed when the ammonia is washed out with water or alcohol. Also here the original cellulose crystal structure is regularly regained.
  • the DE 43 29 937 proposes that, in order to maintain the activation state after the ammonia swelling, under the effect of superheated steam the required residual ammonia should be replaced by water as swelling or inclusion agent. It has been found that the activation state is lost quickly when the material treated in this manner is not immediately processed further.
  • the cellulose after the swelling in liquid ammonia at a low temperature, is not recovered in the dry form but the mixture is mixed with an aqueous alkali hydroxide solution and the ammonia is removed in the presence of the alkalising agent. The obtained alkaline cellulose suspension is immediately subjected to an etherification reaction.
  • the U.S. Pat. No. 5,322,524 describes cellulose fibres or cellulose-containing fibres with an improved resistance to abrasion and an increased permeability with respect to chemicals.
  • the increased permeability leads to an improved activity in respect of chemicals.
  • cellulose fibres are treated in ammonia vapour, between room temperature and 140° C. at about 7 bar (100 psi) to 120 bar (1,700 psi), for a sufficiently long time to change the inter-atomic planar distances in the cellulose and to obtain another modification of the cellulose in the form of stable crystalline cellulose III.
  • the operation is carried out, for example, in a Parr cylinder and the pressure is reduced by opening same. Only ammonia escapes.
  • Cellulose fibres remain behind in the Parr cylinder.
  • the obtained fibres of crystalline cellulose III can be treated in ethylene diamine and can subsequently be subjected to boiling in dimethyl formamide to convert the cellulose III to cellulose IV.
  • the stability of the cellulose III is proved by the fact that after one hour of boiling in water it cannot be converted to cellulose I. It is characterised by a specific X-ray diffraction spectrum with peaks at diffraction angles 2 ⁇ of 11.5, 15.5 and 20.5.
  • the state of the art described in the foregoing corresponds to a large extent to that indicated in the publication "Textile Research Journal", July 1986, p. 419-424.
  • the EP-A-0 077 287 relates to the use of liquid ammonia for activating cellulose contained in animal feeds, using high pressure. According to this the material that contains the cellulose is treated with liquid ammonia at high pressure. Then a quick reduction of the pressure to atmospheric pressure takes place, which causes boiling of the ammonia and a separation into fibres of the cellulose material. The cellulose starting material remains in the system, the internal pressure of which is reduced to atmospheric pressure.
  • the U.S. Pat. No. 3,707,436 proposes a process for producing cellulose for the paper manufacture, with which the lignocellulose material is impregnated with anhydrous ammonia in a closed chamber under pressure and the pressure is suddenly reduced, during which an explosion-like removal of the ammonia and a flinging out of the material takes place.
  • the starting material preferably consists of wood chips which, in addition to cellulose, contain considerable quantities of lignin, hemicellulose and up to 100% water content.
  • the wood chips are impregnated with so much ammonia that the system contains at least the same quantity of ammonia as water, and are heated to a temperature which suffices for their plastification.
  • a mass ratio of ammonia to water in the range of 2 to 4 is used.
  • the hemicelluloses remain behind in the product in the water-insoluble form. They make the material plastic and give strength to the paper products made from same.
  • the obtained cellulose is slightly more amorphous and plastic than in the initial state.
  • the U.S. Pat. No. 5,171,592 describes a process for treating biomasses.
  • the process comprises a.o. the "Ammonia Freeze Explosion” (AFEX), with which the biomass is swollen with liquid ammonia and is then exploded into a flash tank by opening a valve. During the explosion about 25% of the used ammonia are evaporated.
  • the biomass is predried by treating it with superheated ammonia vapour, deaerated and pre-heated. After the AFEX treatment the remaining liquid ammonia is expelled by a treatment with ammonia vapour.
  • cellulose is present accompanied by lignin and hemicelluloses.
  • Biomass furthermore usually contains at least 50% moisture.
  • Lignin is a complex high-polymer natural substance which is embedded in the inter-fibrillary capillary spaces of the cellulose fibres.
  • the fibrillary cellulose chains are joined by a thin cross-linked layer of lignin and hemicellulose to other fibrils to form a fibre bundle.
  • the matrix of lignin and hemicellulose surrounds and protects the cellulose fibrils and holds the structure together, similar to a resin in a composite glassfibre material.
  • this object is achieved by a process which is characterised in that the volume available for the polysaccharide/liquid ammonia system is increased in an explosion-like manner whilst reducing the pressure by at least 5 bar.
  • the term "explosion-like" used here must be understood in the narrow sense.
  • the explosion-like increase in volume takes place within less than one second, in particular less than 0.5 seconds.
  • the process is adapted to an incremental polysaccharide/liquid ammonia quantity.
  • the polysaccharide starting material and the liquid ammonia are preferably brought in contact in a pressure device, and the pressure of the polysaccharide/liquid ammonia system is released by transferring the system into an explosion chamber with a volume larger than that of the pressure device.
  • the starting pressure lies between about 5 and 46 bar and in particular between about 25 and 30 bar. The minimum drop in pressure of 5 bar is critical. Below this value the object of the invention will not be achieved, i.e.
  • the product will not have the desired properties.
  • An excess of the upper limit value of about 46 bar does not produce any further advantages.
  • the use of this pressure requires a relatively high expenditure on equipment, so that a further increase in pressure is not expedient when taking practical considerations into account.
  • the temperature of about 25 to 85° C. and 55 to 65° C., respectively, correlates with the indicated pressure frame.
  • the starting pressure in the polysaccharide/liquid ammonia system is reduced explosion-like by at least about 10 bar and, in particular, by about 30 bar.
  • the explosion preferably takes place in an explosion chamber which is kept under vacuum.
  • the explosion chamber must be chosen sufficiently large to obtain the desired separation into fibres or the defibrillation in the larger volume.
  • An adequate quantity of ammonia must be pressed into the pressure device so that liquid ammonia is present under the pressure and temperature conditions required according to the invention and at least the surface of the polysaccharide starting material is wetted.
  • liquid ammonia for 1 part by mass of polysaccharide at least 1 part by mass of liquid ammonia, in particular at least about 5 parts by mass and especially about 5 to 10 parts by mass of liquid ammonia, are present. Due to the action of the ammonia an at least partial swelling of the polysaccharide starting material takes place.
  • polysaccharides can be activated by the process according to the invention.
  • they are polysaccharides which, because of the formation of inter-molecular hydrogen bridge bonds, have crystalline regions.
  • the polysaccharides may be modified by derivation, cross-linking or conversion.
  • the used polysaccharides have a polyhexose structure, i.e. a structure the monomers of which are C 6 -saccharides.
  • these include the biopolymers starch, cellulose, inulin, chitin and alginic acid, of which cellulose, chitin and starch are preferred.
  • the mentioned polysaccharides each contain only one type of building blocks--even though possibly in changing glycosidic combination--and can, therefore, be counted among the homoglycans.
  • Other polysaccharides that can be activated according to the invention are heteroglycans of various types of monomer units.
  • the preferred heteroglycans include the galactomannans, of which guar gum is particularly preferred.
  • the polysaccharides that are used preferably have a polymerisation degree DP (average number of monomer units bound in the macromolecule) of 500 to 10,000, in particular of 500 to 3,000, but under no circumstances less than 150.
  • DP average number of monomer units bound in the macromolecule
  • a particularly suitable cellulose starting material for carrying out the process according to the invention are chemical pulps in rolls or balls, with a density of about 0.6 to 0.8 g/cm 3 .
  • the polysaccharides used according to the invention preferably are chemically pure. They preferably contain less than 18% by mass, in particular less than 90% by mass foreign substances, such as, in particular, proteins and lignin. In particularly preferred embodiments the polysaccharides contain less than 5% by mass, in particular less than 1% by mass foreign substances. As a rule the used polysaccharides must be free from protein. Too high protein content causes undesirable secondary reactions during the further processing.
  • the degree of activation obtainable according to the invention depends on the water content of the polysaccharide starting material. Too high a water content causes an insufficient activation, which can probably be attributed to the diluting effect of the water molecules on the ammonia.
  • the water content of the polysaccharide starting material therefore, preferably is less than 12% by mass, in particular less than 9% by mass. In particularly preferred embodiments the water content is less than 0.5% by mass.
  • most polysaccharides are hygroscopic and during the storage under ambient conditions absorb water, to maintain a low water or moisture content it may be necessary to subject the polysaccharide starting material to suitable drying steps.
  • the equilibrium water content of most polysaccharides under normal conditions is about 7 to 9% by mass.
  • This change is basically adiabatic but it is also possible at the same time, to supply energy to the system by, for example, heating the explosion chamber.
  • V 2 , p 2 , T 2 preferably more than about 50%, in particular more than 80% of the original liquid ammonia quantity ⁇ .n is present in the gaseous form. Most preferred is a practically complete, sudden evaporation of the liquid ammonia. Since the adiabatic change in state goes hand in hand with a drop in temperature, T 1 must be chosen sufficiently high and/or p 2 sufficiently low to meet this condition.
  • the process according to the invention differs from the "ammonia explosion" process of the state of the art.
  • a drop in pressure is generally produced by opening a valve of an autoclave.
  • a small quantity of the used ammonia for example 20%, evaporates quickly, and the mass treated with liquid ammonia remains behind in the autoclave together with the rest of the ammonia. Due to the occurring cooling effect the mass ruptures.
  • the residual quantity of liquid ammonia boils continuously, the evaporation of the ammonia takes place over a long time.
  • the residual ammonia content of the primary process product is quite high, generally well above 1% by mass.
  • the process according to the invention can be carried out batch-wise or continuously.
  • the apparatus essentially comprises a pressure tank which can be filled with the material to be treated, and a collecting or expansion tank connected to same by way of a valve.
  • the volume of the expansion tank is many times greater than that of the pressure tank, e.g. the volume of the pressure tank is 1 l and the volume of the expansion tank 30 l.
  • the pressure tank is connected to a feed pipe for ammonia, possibly via a pressure-increasing device.
  • a supply pipe for inert gases e.g. nitrogen, can be provided.
  • the process can be carried out in a tubular or cylindrical, pressure-resistant reactor, with which the bringing into contact of polysaccharide and liquid ammonia takes place in the cylinder of the reactor and the impregnated material is moved through the reactor in the form of a wad with the aid of a conveyor worm and is intermittently discharged into a collecting chamber through a valve or a suitable system of pressure locks.
  • Suitable components which the expert can readily adapt for implementing the process according to the invention, are described in the EP-A-329 173 and U.S. Pat. No. 4,211,163, respectively.
  • the contact time between the liquid ammonia and starting material inside the pressure vessel is not critical. It may be very short, e.g. a few seconds. As an expedient time frame about 1 s to 60 min can be indicated, but for polysaccharides that are difficult to swell it may also be much longer. A contact time of less than 1 s can hardly be realised for practical reasons. A treatment of more than 60 minutes generally does not produce any further technical advantage. Contact times in the range from 10 s to 1 minute are generally preferred.
  • the gaseous ammonia is drawn off, preferably liquefied to liquid ammonia and then fed back into the process.
  • the polysaccharide is preferably subjected to a heat treatment and/or vacuum treatment to reduce the residual contents of water and ammonia.
  • Optimal results are obtained, for example, at a temperature of 60° C. and a pressure of 10 mbar over 2 h. In this way the residual water content can be reduced to less than 1% by mass and the residual ammonia content to less than 0.2% by mass.
  • cellulose has a spatial network structure in which the elementary fibrils are associated over a specific length into fibrillary aggregates.
  • the aggregation degree and the aggregation length are important structural characteristics.
  • the simplest method for determining the length of these elements in cellulose fibres consists of examining the course of the heterogeneous hydrolytic decomposition.
  • An activated cellulose obtained according to the invention occurs in the form of fluff.
  • This is characterised in that it has a favourable LODP-value for the various derivation measures.
  • This value preferably lies between about 50 and 200, in particular between about 100 and 160 and especially preferred between about 120 and 145.
  • the mentioned framework of LOPD-values which are associated with preferred embodiments of the invention, is an indication of the improved accessibility of the fluff according to the invention for, for example, derivation reagents.
  • the cellulose fluff according to the invention is furthermore characterised by a not as yet attained low density of less than about 0.2 g/cm 3 . In this a reason can be seen for its special activity during the indicated derivation processes. This advantage is increased when the density of the fluff is less than 0.1 g/cm 3 . It is a special dimensional figure and furnishes information about the extent of the explosion treatment.
  • the particularly high activity during the various derivation processes can above all be attributed to the fact that the fluff or the fibres forming same are more accessible to the chemicals that are used. This leads to shorter reaction times and to a low consumption of chemicals. Furthermore, more homogeneous derivation products are obtained.
  • acylation e.g. acetylation, silylation, xanthogenation or production of carbamates and alkylation by etherification with alkyl halogenides, epoxy compounds, unsaturated organic compound (Michael addition) and the like.
  • This list of derivation processes is not limiting.
  • the mentioned advantage of improved accessibility can also be utilised for any other derivation processes.
  • a cellulose activated according to the invention is characterised in that it has an X-ray diffraction spectrum with peaks of the indicated relative intensities at the following diffraction angles 2 ⁇ and with the relative intensities:
  • a special characteristic of the cellulose fluff according to the invention consists of the demarcation from the state of the art described at the outset because, during the boiling in water under atmospheric pressure for at least one hour it is again to a large extent converted back to cellulose I. This is in strict contradiction to the information of the U.S. Pat. No. 5,322,524 about the material described there.
  • ammonia content of the cellulose fluff according to the invention is less than about 0.5% by mass.
  • the cellulose fluff according to the invention is furthermore characterised in that it can be produced with a desirable low water content of less than about 6% by mass, in particular less than 1% by mass. Accordingly, during the practical implementation of the teachings of the invention the water content can without problem be reduced to below the value of commercial cellulose materials. These normally contain about 6 to 7% water. If the consumer is offered a material with a water content of, in particular, less than 1% by mass, this means a reduction in the transport costs and a considerable reduction in the consumption of chemicals during, for example, the acylation.
  • Guar gum activated according to the invention and compounds obtained from same by derivation when used as thickening agents, stand out by, for example, advantageous rheological properties.
  • Aqueous solutions thereof, in contrast to untreated forms, display a viscosity which is largely independent of a shearing effect.
  • Guar gum derivatives which are activated according to the invention prior to the derivation moreover display a favourable redispersability after the drying, which is advantageous when printing textiles using thickened dye pastes.
  • a further application of the process according to the invention is the activation of chitin.
  • Chitin normally occurs in smooth hard particles which are very difficult to dissolve in solvents.
  • a morphological change takes place, during which the surface is roughened and the particles are expanded.
  • the accessibility to chemicals and/or solvents is decisively improved.
  • From chitin activated according to the invention by a partial de-acetylation to chitosan, interesting and until now difficult to obtain products can be produced for use in the cosmetics, medicine, food-technology and chemical-technical fields.
  • a product which stands out by particularly advantageous properties. It has an unusually low density. This assists among others the derivation reactions, e.g. within the framework of the alkylation, acylation, silylation and xanthogenation, seeing that the polysaccharides activated according to the invention are better accessible to derivation agents. This reduces the reaction time and the consumption of chemicals. A reason for the improved reactivity may also lie in the special chemical-structural properties of the products according to the invention.
  • Level-off DP of cellulose 590 ml denatured ethyl alcohol are mixed with 30 ml concentration sulphuric acid and heated for 30 minutes under reflux on the water bath. After cooling, for control purposes the sulphuric acid content is determined, which must be about 5.8%. 500 mg of the to be tested cellulose sample with 30 ml of the ethanolic sulphuric acid are heated for 7 hours to boiling point (82° C.) on the water bath in a 100 ml round flask provided with a reflux cooler. Then the cellulose is separated from the ethanolic sulphuric acid on a frit, washed first with water and then with ethanol, and the DP of the dried, hydrolytically decomposed cellulose is determined.
  • the DP-value was determined by the Cuoxam method.
  • Acetylation test With this test the temperature pattern during the acetylation of cellulose samples is examined. The following method was used: 200 g of the to be tested cellulose are mixed in a 2 l flask with 800 ml acetic acid and 1.0 ml sulphuric acid which beforehand were heated to 70° C., and kept on a heated roller bank at 45 to 50° C. After about 1.5 h the melting point of the acetic acid is determined, and from this the quantity of acetic acid anhydride required for the drying is calculated. After a further 30 minutes at 45 to 50° C., the calculated quantity of anhydride is added and the mixture is cooled to 20 to 22° C.
  • the mixture is mixed with 500 ml acetic acid anhydride in a Dewar vessel whilst stirring continuously. From the moment when the anhydride is added, the change in temperature is recorded by a X-Y recorder in dependence on the time. The determination is ended when the temperature starts to drop.
  • ammonia content of the product occurring in the explosion chamber amounted to about 1% by weight related to the defibrillated cellulose material.
  • the gaseous ammonia was drawn off by applying a vacuum, which caused the ammonia content to drop to 0.2% by mass.
  • FIG. 1 shows the X-ray spectrum of Sample A according to the invention, Example 1, Sample B in which the material was subjected to heat and contained no residual ammonia content, Sample C in which the material was treated with water leading to a partial conversion back to the untreated sample. Sample D is a comparison with material treated with aqueous ammonia and Sample E is untreated cellulose;
  • FIG. 2 is a temperature time graph and comparison in the acetylation reaction of the samples according to the invention which proceeded homogeneously and samples F, G and H which contained 30.7% water;
  • FIG. 3 shows the comparison in viscosity of the carboxymethylated product previously activated according to the invention, and a product not activated according to the invention.
  • Sample A is a cellulose activated as in example 1. The residual ammonia content was less than 0.5% by mass. Sample B was subjected to a heat treatment and no longer contained any detectable residual ammonia content. Sample C was treated with water at 80° C. for 60 minutes. Sample D is a comparison cellulose which was treated with aqueous ammonia solution (ratio of aqueous NH 3 /cellulose 10:1) and then dried. Comparison sample E is untreated cellulose.
  • the X-ray spectrum of sample A treated according to the invention differs clearly from those of the comparison samples D and E.
  • the X-ray spectrum of sample B shows that by a drying and heat treatment, respectively, whilst removing the residual ammonia content, no change in the structure occurs.
  • the treatment with warm water shows a return of the new cellulose modification produced by the ammonia explosion in the direction of the initial modification.
  • the X-ray spectrum of the untreated cellulose material E corresponds substantially to the spectrum of the cellulose I.
  • crystal Index the degree of crystallinity (Crystal Index, CrI)
  • Hans A. Krassig Polymer Monographs", Vol. II, Gordon and Breach Science Publishers, p. 89.
  • guar gum 50 g guar gum (powdered, water content about 7.9%, protein content about 4%) were put into an autoclave with a volume of 1 l and a double wall for steam heating.
  • 280 g liquid ammonia were pressed into the autoclave through a valve. By steam heating the autoclave the temperature was raised to 60° C. By doing so a pressure of 30 bar occurred. The system was kept under these conditions for 30 minutes.
  • the guar gum/liquid ammonia system was pressure relieved suddenly and completely into an explosion tank with a volume of 100 l. The water content after the explosion was 2.6%.
  • the process product was collected and dried at 60° C. The residual ammonia content was 1% by mass.
  • FIG. 3 shows the viscosity curves (viscosity as function of the shear rate expressed as rpm) of a 1% solution in water of a carboxymethylated guar gum without pre-treatment (K) and of the carboxymethylated ammonia-exploded guar gum (L).
  • the viscosity curve of the guar gum activated according to the invention prior to the carboxymethylation is clearly flatter than that of the comparison product. It has a much longer Newton range, i.e. the change in viscosity at low shear rates is less than with the comparison product. At a low shear rate the viscosity is clearly lower.
  • This example shows the use of the carboxymethylated guar gum produced in example 5 as a thickening agent for printing textiles.

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  • General Health & Medical Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
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US6348590B1 (en) * 1996-12-23 2002-02-19 Rhodia Acetow Ag Method for improving the exploitability and processability of guar endosperm and products obtained using said method
US20040116213A1 (en) * 2002-12-06 2004-06-17 Filosa Michael P. Water-immersion indicator indicia and articles bearing such indicia
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US11692000B2 (en) 2019-12-22 2023-07-04 Apalta Patents OÜ Methods of making specialized lignin and lignin products from biomass
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19628277C2 (de) * 1996-07-12 1998-07-09 Rhodia Ag Rhone Poulenc Verfahren zur Aktivierung eines Cellulose und Harnstoff enthaltenden Gemisches, aktiviertes Cellulose und Harnstoff enthaltendes Gemisch und Verwendung des aktivierten Gemisches zur Herstellung von Cellulosecarbamat
DE19742692A1 (de) * 1997-09-26 1999-04-01 Rhodia Acetow Ag Verfahren zur Aktivierung von Polysacchariden
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DE19810740A1 (de) * 1998-03-13 1999-09-16 Rhodia Acetow Ag Verfahren zur Dosierung eines Ammoniak/Zusatzstoff-Systems in einen Feststoff und Dosiervorrichtung
DE19814137A1 (de) * 1998-03-30 1999-10-14 Rhodia Acetow Ag Verfahren zum Austreiben von Ammoniak aus einem aktivierten Polysaccharid
DE19921755A1 (de) * 1999-05-11 2000-11-16 Rhodia Acetow Ag Verfahren zur Herstellung einer Spinnlösung von Zellstoff in N-Methylmorpholin-N-oxid-Monohydrat, die damit erhältlichen Lösungen sowie die daraus durch Verspinnen erhältlichen Regeneratcellulosefasern
MX2012006961A (es) * 2009-12-17 2012-10-03 Fina Biosolutions Llc Reactivos quimicos para la activacion de polisacaridos en la preparacion de vacunas conjugadas.
JP2012080818A (ja) * 2010-10-12 2012-04-26 Idemitsu Kosan Co Ltd 固体バイオマスの糖化前処理方法、その装置、および、固体バイオマスの糖化方法
CN103145873B (zh) * 2011-12-06 2015-12-09 蔡敏郎 几丁质去乙酰化的方法
EP3196205A1 (en) * 2016-01-22 2017-07-26 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Etherification of carbohydrates using superheated steam

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD98322A1 (es) * 1972-07-17 1973-06-12
SU914563A1 (ru) * 1980-04-04 1982-03-23 Inst Khim Drevesiny An Latssr Способ активации целлюлозы 1
DE3241720A1 (de) * 1982-11-11 1984-05-17 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von celluloseethern aus mit ammoniak aktivierter cellulose
US4600590A (en) * 1981-10-14 1986-07-15 Colorado State University Research Foundation Method for increasing the reactivity and digestibility of cellulose with ammonia
US5037663A (en) * 1981-10-14 1991-08-06 Colorado State University Research Foundation Process for increasing the reactivity of cellulose-containing materials
US5473061A (en) * 1993-09-04 1995-12-05 Rhone-Poulenc Rhodia Aktiengesellschaft Process for the treatment of cellulose

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171592A (en) * 1990-03-02 1992-12-15 Afex Corporation Biomass refining process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD98322A1 (es) * 1972-07-17 1973-06-12
SU914563A1 (ru) * 1980-04-04 1982-03-23 Inst Khim Drevesiny An Latssr Способ активации целлюлозы 1
US4600590A (en) * 1981-10-14 1986-07-15 Colorado State University Research Foundation Method for increasing the reactivity and digestibility of cellulose with ammonia
US5037663A (en) * 1981-10-14 1991-08-06 Colorado State University Research Foundation Process for increasing the reactivity of cellulose-containing materials
DE3241720A1 (de) * 1982-11-11 1984-05-17 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von celluloseethern aus mit ammoniak aktivierter cellulose
US5473061A (en) * 1993-09-04 1995-12-05 Rhone-Poulenc Rhodia Aktiengesellschaft Process for the treatment of cellulose

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Peng et al. Hsin Hsien Wei , vol. 22(9): 13 14, (1980). ** *
Peng et al. Hsin Hsien Wei, vol. 22(9): 13-14, (1980). **

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US20040116213A1 (en) * 2002-12-06 2004-06-17 Filosa Michael P. Water-immersion indicator indicia and articles bearing such indicia
US6881252B2 (en) 2003-09-23 2005-04-19 Corn Products International, Inc. Fiber-based product
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US9476077B2 (en) 2012-06-11 2016-10-25 Codexis, Inc. Fungal beta-xylosidase variants
US8980578B2 (en) 2012-06-11 2015-03-17 Codexis, Inc. Fungal beta-xylosidase variants
US9650655B2 (en) 2012-07-20 2017-05-16 Codexis, Inc. Production of fatty alcohols from engineered microorganisms
CN102976802A (zh) * 2012-11-23 2013-03-20 山东嘉丰海洋生物科技有限公司 一种壳聚糖液体肥料的加工方法
CN102976802B (zh) * 2012-11-23 2014-09-03 山东嘉丰海洋生物科技有限公司 一种壳聚糖液体肥料的加工方法
US9512447B2 (en) 2012-12-14 2016-12-06 Codexis, Inc. Modified native beta-ketoacyl-ACP synthases and engineered microorganisms
US9809867B2 (en) 2013-03-15 2017-11-07 Sweetwater Energy, Inc. Carbon purification of concentrated sugar streams derived from pretreated biomass
US9909078B2 (en) 2013-08-20 2018-03-06 Biomass Energy Enhancements, Llc Microwave produced pyrolysis oil from beneficiated organic-carbon-containing feedstock
US9422481B2 (en) 2013-08-20 2016-08-23 Douglas M Van Thorre Microwave produced pyrolysis oil from beneficiated organic-carbon-containing feedstock
US9593447B2 (en) 2013-08-20 2017-03-14 Biomass Energy Enhancements, Llc System and method using a reaction chamber to beneficiate organic-carbon-containing feedstock for downstream processes
US9796940B2 (en) 2014-06-16 2017-10-24 Biomass Energy Enhancements, Llc Processed biomass pellets from organic-carbon-containing feedstock
US10018355B2 (en) 2014-06-16 2018-07-10 CTP Biotechnology, LLC System and process for combusting coal and beneficiated organic-carbon-containing feedstock
US10024533B2 (en) 2014-06-16 2018-07-17 Ctp Biotechnology Llc System and process for combusting cleaned coal and beneficiated organic-carbon-containing feedstock
US9683738B2 (en) 2014-06-16 2017-06-20 Biomass Energy Enhancements, Llc System for co-firing coal and beneficiated organic-carbon-containing feedstock in a coal combustion apparatus
US9701918B2 (en) 2014-06-16 2017-07-11 Biomass Energy Enhancements, Llc System of using a reaction chamber to beneficiate organic-carbon-containing feedstock for downstream processes
US9702548B2 (en) 2014-06-16 2017-07-11 Biomass Energy Enhancements, Llc System for co-firing cleaned coal and beneficiated organic-carbon-containing feedstock in a coal combustion apparatus
US10844413B2 (en) 2014-12-09 2020-11-24 Sweetwater Energy, Inc. Rapid pretreatment
US11299723B2 (en) 2016-06-15 2022-04-12 Codexis, Inc. Engineered beta-glucosidases and glucosylation methods
WO2018106656A1 (en) 2016-12-06 2018-06-14 Danisco Us Inc Truncated lpmo enzymes and use thereof
US11821047B2 (en) 2017-02-16 2023-11-21 Apalta Patent OÜ High pressure zone formation for pretreatment
US11692000B2 (en) 2019-12-22 2023-07-04 Apalta Patents OÜ Methods of making specialized lignin and lignin products from biomass

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EA000169B1 (ru) 1998-10-29
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WO1996030411A1 (de) 1996-10-03
JPH10505130A (ja) 1998-05-19
RO115053B1 (ro) 1999-10-29
EP0817803A1 (de) 1998-01-14
KR19980703294A (ko) 1998-10-15
BR9607992A (pt) 1999-11-30
JP3390015B2 (ja) 2003-03-24
EP0817803B1 (de) 1999-06-16
ES2135221T3 (es) 1999-10-16
CA2214245C (en) 2001-10-02
EA199700268A1 (ru) 1998-02-26
BG62778B1 (bg) 2000-07-31
AU695331B2 (en) 1998-08-13
PL322468A1 (en) 1998-02-02
AU5148196A (en) 1996-10-16
KR100254840B1 (ko) 2000-05-01
CZ300597A3 (en) 1997-12-17
DE19611416A1 (de) 1996-09-26
JP2002161101A (ja) 2002-06-04
CN1083454C (zh) 2002-04-24
ZA962370B (en) 1996-10-07
DE59602248D1 (de) 1999-07-22
CN1179781A (zh) 1998-04-22
SK128597A3 (en) 1998-03-04
HUP9802337A2 (hu) 1999-02-01
ATE181338T1 (de) 1999-07-15
CA2214245A1 (en) 1996-10-03

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